Crystal and molecular structure of bis(2-pyridine sulfinato)copper(II)

Higashi, Lois S.; Lundeen, Munime; Hilti, Ernst.; Seff, K.

doi:10.1021/ic50168a017

Cited by 53 publications

(43 citation statements)

References 37 publications

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“…The shift of the 1594 cm À1 band to higher energy with respect to free ligand (1570 cm À1 ) indicates coordination to the metal through the pyridine nitrogen. The sulfinate-sulfonate groups show strong bands in the region 1280-1050 cm À1 assigned to (S-O) vibrations with coordination to copper(II) ion through oxygen atom and are similar to those observed in sulfinate [7] and sulfonate [8] analogous complexes.…”

supporting

confidence: 60%

“…It is known that the oxidation of 2,2 0 -dipirydyldisulfide to pyridine-2-sulfinate in the presence of the cupric perchlorate and water, under both aerobic and anaerobic conditions, leads to the molecular complex [Cu(2-pySO 2 ) 2 ] [7]. In general, further oxidation of disulfides or sulfinate compounds to the corresponding sulfonates requires a strong oxidising agent such as hydrogen peroxide or halogen [10], though the aerial oxidation of 2,2 0 -bis(3-methylpyridyl)disulfide with CuBr 2 afforded the one-dimensional polymer [{Cu(3-mpySO 3 ) 2 } n ] in low yield [9].…”

mentioning

confidence: 99%

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An unexpected sulfinate–sulfonate mixed coordination polymer of copper(II)

Delgado¹,

Molina‐Ontoria²,

Medina³

et al. 2006

Inorganic Chemistry Communications

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supporting

confidence: 60%

mentioning

confidence: 99%

An unexpected sulfinate–sulfonate mixed coordination polymer of copper(II)

Delgado¹,

Molina‐Ontoria²,

Medina³

et al. 2006

Inorganic Chemistry Communications

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“…Although heterocyclic disulfide ligands such as 2-dpds or 3-mpds (3-mpds = 2,2′-bis(3-methylpyridyl)disulfide) can also experience such a reaction, they are exclusively promoted by CuX 2 salts (X = ClO 4 , or Br). [10][11][12] To the best of our knowledge, such a Ag(I)-mediated reaction of heterocyclic disulfide is still rare. Although oxidant under basic conditions, 26 the present reaction provides a mild (ambient conditions) and environment-benign (H 2 O as O atom source) approach.…”

Section: Agno 3 -Mediated In Situ Reaction Of 2-ppdsmentioning

confidence: 99%

Unprecedented metal-mediated in situ reactions of heterocyclic disulfide of di[4-(pyridin-2-yl)pyrimidinyl]disulfide

Zhu

Zhao

et al. 2014

Dalton Trans.

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By the combination of different metal salts and solvents, four unprecedented in situ reactions have been discovered for heterocyclic disulfide of 2-ppds (2-ppds = di[4-(pyridin-2-yl)pyrimidinyl]disulfide). In the CH3CN-DMF solvent, reaction of 2-ppds with AgNO3 produced a one-dimensional chain structure of {[Ag2(1L)2]·2CH3CN}n (1), wherein 2-ppds was converted into its sulfonate of 1L by means of oxidative cleavage of the S-S bond. In the CH3CN-DCM solvent, reaction between 2-ppds and Cu(ClO4)2 yielded a discrete mononuclear Cu(II) coordination structure of [Cu(2L)2H2O)](ClO4)2 (2), of which 2-ppds was turned into a totally unexpected zwitterion product of 2L via C-S bond scission followed by O substitution. In the MeOH-DCM solvent, reaction of 2-ppds with Co(ClO4)2 resulted in a mononuclear Co(III) coordination structure of [Co(3L)2]ClO4·2CH3OH·H2O (3), in which 2-ppds was transformed into its persulfide of 3L via selective single C-S bond rupture. In the CH3CN-DMF solvent, reaction between 2-ppds and CuI afforded a binuclear mixed-valence Cu(I)Cu(II) coordination structure of [Cu2I(4L)2] (4), wherein 2-ppds was converted into its thiolate of 4L through homolytic S-S bond cleavage. The reaction mechanisms of these reactions have also been discussed on the basis of these in situ generated coordination structures coupled with our previous observations on 2-ppds.

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“…In fact, the earliest report, dating back to 1977, revealed that reaction of 2-dpds with Cu(ClO 4 ) 2 yielded a yellow product and a green product, which were structurally determined as a Cu I -disulfide complex and bis(2-pyridinesulfinate) copper(II) complex, respectively [16]. In this reaction, 2-dpds is believed to be oxidized into 2-pyridinesulfinato by Cu(II) ions, which may proceed by a concomitant electrophilic and nucleophilic attack on the S-S bond by the Cu(II) ion and water molecules (Scheme 14).…”

Section: Under Ambient Conditions In Solutionmentioning

confidence: 99%